Method for preparing supported catalytic structures



United States Patent M 3,228,892 METHOD FOR PREPAG SUPPORTED CATALYTIC STRUCTURES Edward L. Cole, Glenham, and Edwin C. Knowles,

Poughkeepsie, N.Y., assignors to Texaco Inc., New

York, N .Y., a corporation of Delaware No Drawing. Filed Dec. 29, 1960, Ser. No. 79,183

3 Claims. (Cl. 252463) This invention relates to a catalytic structure and, more particularly, is concerned with the preparation of improved supported catalysts.

During catalytic processing with solid particulate catalysts, the reactants are passed through a bed of porous catalyst particles, beads or pellets. In many such reactions employing organic materials at elevated temperatures, a carbonaceous deposit accumulates on the catalyst surface and in the pores and openings of the catalyst as the process proceeds under continuous operating conditions. This deposition of carbonaceous material, commonly known as fouling of the catalyst, is a function of the reactants, the reaction products, the conditions of the process, and the catalyst, and certain types of reactions may be worse offenders than others. Fouling may be particularly excessive when the reactants or products remain in contact with the catalyst for a relatively long time. When a porous catalyst is used, the reactants diffuse into the interior of central portion of the catalyst particle and may be retained for an excessive period of time whereupon decomposition of the reactants and products result in fouling the catalyst. Fouling results not only in a decrease in catalyst activity and loss in selectivity, but also results in intensification of the heat transfer problem in the catalyst bed thereby resulting in local overheating or hot spots, particularly during regeneration of the catalyst.

Heat transfer and temperature control in a catalyst bed often are diflicult problems by reason of the heat of reaction which accompanies numerous catalytic reactions. Thus, in an exothermic reaction, for example, the heat evolved in processing may result in formation of local overheating or hot spots unless distributed substantially uniformly throughout the catalyst bed or otherwise dissipated from the reaction zone. Generally it is desirable, or essential, to maintain the reaction temperature within a predetermined range in order to obtain the maximum yield of desired products. Local overheating and temperature variations in the catalyst bed are therefore deleterious and may result in excessive coking of the reactants, inactivation of the catalyst, or otherwise cause undesired side reactions.

The catalyst bed, customarily provided in a composite form comprising an active component supported by a carrier, is generally a relatively poor conductor of heat. Temperature control may be particularly difficult in a conventional packed column or fixed bed reactor where each layer of catalyst is, in effect, partially insulated from adjacent layers. Heat carriers or heat conductive materials have been proposed as one means of reducing temperature gradients in a catalyst bed. For carrying out some highly exothermic or highly endothermic reactions, it has been proposed to incorporate pieces of metal or other suitable heat conductive solid material in the fixed catalyst bed to facilitate heat transfer to the surroundings. Heat transfer and temperature control of the catalyst bed have been achieved by employing a gaseous or liquid heat-transfer medium usually circulated through a jacket surrounding the reactor. The reactants may be diluted with steam or in inert gas as a further means of achieving temperature control. However, the known or proposed methods regarding thermal control necessitates especially Patented Jan. 11, 1966 designed reactors, and further may require materials and equipment in addition to that normally employed.

In certain processing operations, the temperature may be controlled within the desired range by employing low flow rates or low conversion levels to limit the rate of heat released by the reaction. However, this normally results in a corresponding decrease in yield per unit of time. Notwithstanding this precaution, uncontrollable local overheating and temperature variations in the catalyst bed may occur.

This invention has therefore a its purpose to provide a method for preparing catalytic structures capable of operating under substantially isothermal conditions and characterized by relatively high activity over long periods of use in any of a wide variety of chemical reactions. The catalytic structure produced by the method of this invention is provided with an extended metal substrate exhibit ing relatively high thermal conductivity which affords an effective means for adequately controlling the thermal conditions of the reaction thereby minimizing, or subtsantially eliminating, temperature variations in the catalyst bed and local overheating and fouling. Equally important, our catalytic structure is not restricted to any particular configuration, and may comprise the walls of the reactor thereby obviating the need for employing a packed column of catalyst. As a result, the quantity of active catalyst material used in our catalytic structure is greatly reduced as compared to the quantity required in conventional structures. This eliminates a substantial portion of the structural and supporting members of the reactor, permits compactness in design and decreases substantially the capital costs and operating costs. It i significant that the foregoing and other objects are realized without diminishing the flow rates of the reactants, but, on the contrary, in many catalytic processes, the reaction rates may be greatly increased without any appreciable decrease in product yield. These together with other objects and advantages will be apparent to one skilled in the art upon reading the following description.

The novel catalytic structure of our invention involves broadly an extended metal substrate exhibiting relatively high thermal conductivity and capable of readily forming an adherent oxide coating or film. Metals found most useful include those selected from the group consisting of aluminum, tantalum, titanium, zirconium and hafnium. A catalyst material is deposited upon the oxide film integral with the substrate, which material may be deposited in a form possessing catalytic activity or capable of being rendered susceptible of catalytic activity by subsequent treatment, as explained more fully hereinbelow. Depending to a large extent upon the catalyst material employed, our invention was found to be extremely advantageous and economical for use in a number of catalytic processes, conducted either in liquid or vapor phase.

In accordance with the invention, the metal substrate which is to be employed in the catalytic structure is first provided with an adherent oxide film, preferably a relatively porous and adsorbent oxide film, which serves as the catalyst carrier. The metal substrate is of extended dimensions and is particularly of a length and geometric surface area substantially greater than that of discrete particles. Metals found most useful and susceptible of rendering the desired oxide film include those selected from the group consisting of aluminum, tantalum, titanium, zirconium and hafnium, and more preferably aluminum, tantalum and titanium. As used herein, this is intended to include a pure metal, a commercial metal containing the usual impurities and a base alloy of the metal.

The oxide film may be produced by any of several known methods, including chemical and electro-chemical methods, but must be of suflicient thickness to provide adequate adsorptive capacity for retaining the catalyst deposit. To insure adequate performance under the conditions encountered in catalytic processing, however, the artificially produced oxide film generally should not be substantially thinner than about 0.1 mil, and preferably not less than about 0.5 mil, usually about 0.5 to 1 mil being desirable. Where an aluminum metal substrate is employed, for example, the oxide film may be produced by treating the aluminum surface 'with a solution of an alkaline carbonate, usually a sodium carbonate-chromate solution. The film may be produced by the anodic oxidation of the metal surface whereby the metal is made the anode in an electrolytic solution. In anodizing aluminum, a 15% sulfuric acid solution is commonly employed as the electrolyte, but other acid electrolytes such as chromic acid, oxalic acid, phosphoric acid and sometimes boric acid may be used. Titanium, tantalum, hafnium and zirconium may be anodized advantageously in a boric acid-ammonia solution having a pH of about 8. In all cases the oxide film to which this invention relates is produced by artificial means and does not include relatively thin natural oxide films occurring on metal surfaces which have been exposed to the atmosphere.

The present invention is particularly applicable to anodic films, and more especially to aluminum surfaces having an anodically produced film, and therefore will be described in more detail in connection with films of this type. Oxide films formed by this well-known commercial method are relatively porous and adsorbent, and though this constitutes a preferred embodiment of our invention, it should be understood that other conversion films, including barrier type films, are also useful in the preparation of the catalyst structure of our invention.

The method utilized in depositing the catalyst material upon the oxide film is dependent to some extent upon the particular catalyst material employed. In one method, the catalyst material is deposited by chemically reducing a solution containing a soluble compound of the catalyst material in the presence of the metal substrate bearing the oxide film under such conditions as to eifect a substantially uniform deposition of the catalyst material upon the oxide surface. Although the exact form of the deposit of catalyst material cannot be definitely determined, it is believed that the material is deposited from solution as elemental metal or as its intermediate product ofreduction, such as the oxide. Chemical reduction of the deposit is particularly useful in those instances where the elemental metal or its intermediate product of reduction, exhibits the required catalytic activity, or where a deposit of the metal may be rendered active upon subsequent treatment. In several cases, a compound of the metal forms with a stabilizing agent a soluble complex which may be readily reduced to the elemental metal or its intermediate product of reduction with a suitable reducing agent, preferably a reducing gas, for example, hydrogen. Suitable stabilizing agents include complexing agents which form soluble complex ions of the coordinate complex type, sequestering agents, chelating agents, dispersants and detergents. Thus, compounds or salts of numerous metals form with ammonia, for example, a co-ordination type complex. These metals usually include those from Groups I, VI and VIII of the Periodic Table of Elements, for example, copper, silver, gold, chromium, molybdenum, tungsten, iron, cobalt, nickel, platinum, palladium, osmium and iridium, but may also embrace other elements including those from Groups II, III, IV, V and VII of the Periodic Table, for example, zinc, cadmium, mercury, tin, zirconium, vanadium and manganese, and combinations thereof. The deposit is generally calcined and activated by subsequent treatment, for example, oxidizing or sulfiding of the catalyst metal or metals.

The non-metallic ion or the anion of the metal compound or salt to be precipitated from the ammoniacal solution may be of any inorganic acid or strong organic acid which forms a soluble salt of the metal and is not reduced under precipitation conditions. Those anions usually employed include sulfate, chloride, nitrate, carbonate, chromate and vanadate, and the organic anion generally being acetate. The solvent generally used is an aqueous solution, but suitable organic solvents, including alcohols, aldehydes, ethers, ketones, toluene and pyridine may be used, as may liquid ammonia.

Although ammonia is the preferred stabilizing agent and the invention is described in greater detail in connection with solutions of this type, certain other stabilizing agents may be employed. Other suitable stabilizing agents include the organic primary, secondary and tertiary amines such as methyl amine, ethylenediamine and diethylenetriamine. In addition, stabilizing agents may include phosphates, especially pyrophosphate and metaphosphate, as well as citrate, acetate, oxalate, tartrate, o-phenanthroline, thiocyanate, thiosulfate, thiourea, pyridine, quinoline and cyano groups. Still further useful complex formations include the chloro, hydroxo and aquo complexes, such as the aquo-ammonia complexes. Olefin and olefin-like compounds are also useful, and may include, for example, ethylene, propylene, butadiene, etc., as well as the unsaturated cyclo compounds such as cyclohexene and styrene. However, the olefin and olefin-like compounds are desirably employed in a non-aqueous solvent, for example, benzene, toluene, pyridine, acetone and ether.

The catalyst material may be deposited on the oxide film by the action of a reducing agent, preferably hydrogen, on a solution containing a soluble complex of the catalyst material, such as an ammoniacal solution of a salt of the catalyst material. The temperature and pressure employed in the reducing step depend upon the material undergoing reduction and may vary over a Wide range. Thus, for example, platinum may be deposited from ethylene chloroplatinate in benzene by reduction with hydrogen at room temperature and atmospheric pressure. However, with numerous other metals, reduction proceeds advantageously at elevated temperatures which may range up to 500 F. and under a partial pressure of as high as 4000 pounds per square inch or higher. This procedure is described and claimed in our United States Patent 3,155,627 filed concurrently with this application. To effect a substantially uniform, adherent deposit of the catalyst material upon the oxide film of a metal substrate of extended surface area, it is especially desirable that reduction and deposition proceed under a substantially quiescent condition, i.e., the system is maintained substantially free from turbulence. This procedure is disclosed and claimed in our United States Patent 3,147,154, issued on our copending application Serial No. 112,508 filed May 25, 1961.

It should be understood that other reducing gases such as carbon monoxide may be used with satisfactory results, as may other reducing agents such as hydrazine, hydroxylamine, glyoxal, formaldehyde or sulfur dioxide.

By way of example, elemental platinum useful as a reforming catalyst may be deposited on the oxide film of the support member from an ammoniacal solution of a platinum salt, e.g. the chloride salt or chloroplatinic acid, by reducing the solution with hydrogen at elevated temperature and pressure. Similarly, a silver deposit useful as a catalyst in the oxidation of ethylene may be formed on the oxide film of the substrate from an ammoniacal solution of silver sulfate. On the other hand, a deposit of nickel or of molybdenum similarly formed may be sulfided with hydrogen sulfide gas at elevated temperature, and the sulfide catalyst formed then used in hydrogenation processes. A deposit of chromium may be oxidized for use as a catalyst in polymerization of olefins, or a deposit of iron may be oxidized for use in the reaction of carbon monoxide with hydrogen to produce hydrocarbons.

A mixture of metal salts, all of which form. complex ions With ammonia, may be used for forming a deposit of more than one catalytic element. By such means, a nickeLmoly-bdenum catalyst or cobalt-molybdenum-nickel catalyst may be deposited on the oxide film for use as hydrogenation catalysts. Also, nickel-molybdenum or nickel-tungsten salts may be complexed in a citrate solution, and precipitated from solution with hydrogen as described above. The co-deposits may then be calcined or otherwise activated.

As an alternative procedure, the added catalyst material may be impregnated on the oxide film by contacting the oxide coated substrate with a solution containing the catalyst material. Generally, this is accomplished by immersing the coated substrate in a solution of a salt of the catalyst material. The conditions for impregnating, i.e., concentration, temperature, time and pH, will depend largely upon the material employed and upon the amount of catalyst material required. The deposit is then calcined and activated in place as by oxidizing, reducing, sulfiding, etc. By this method, the oxide film may be impregnated with such catalyst material as salts or compounds of metals from Groups I through VIII of the Periodic Table, and particularly Groups I, IV, VI and VIII, including for example, copper, silver, zinc, tin, vanadium, chromium, molybdenum, manganese, cobalt and iron. By way of illustration, the oxide film may be impregnated with ammonium chromate from an aqueous solution of the salt and the deposit subsequently calcined to form the oxide which is useful in the dehydrogenation of cyclohexane to benzene. The catalyst material may include, as Well, phosphate, metaphosphates, perborates, chromates, perchromates, carbonyls, carbonates, thiocyanates, vanadates, etc. Copper pyrophosphate may be impregnated on the oxide film, calcined, and used as a catalyst in the hydration of ethylene to acetaldehyde.

Although aqueous solutions are usually employed, the catalyst material may be impregnated on the oxide carrier from a non-aqueous solution, particularly acetone, ethanol and the like. Thus, for example, the oxide film may be impregnated with molybdenum blue from an acetone solution of the salt or with zinc chlorate hexahydrate dissolved in alcohol. The molybdenum deposit, upon calcining, may be a useful catalyst in the hydrogenation of lube oil and the zinc deposit, after calcining, may be employed in the dehydration of alcohol to an olefin. In addition, the catalyst material may be impregnated onto the oxide carrier from the vapor phase, as for example by thermally decomposing a metal carbonyl, such as molybdenum hexacarbonyl, and the deposit calcined to the oxide which, in turn, may be sulfided by conventional practice.

In still another method, the catalyst material may be deposited on the oxide filrn by pasting as from a slurry of the material. Zinc oxide, for example, useful as a dehydrogenation catalyst, may be pasted on the oxide coated substrate, and then calcined for use as a catalyst. A co-deposit of aluminum oxide and aluminum nitrate may be pasted on the oxide film from a slurry of the material. After calcining, the co-dep-osit may be used in the dehydration of an alcohol or in the cracking of a hydrocarbon.

In order to assure deposition of the desired quantity of the catalyst material, it may be necessary in some cases to repeat the particular process employed in depositing the material, including the successive steps of deposition, and drying or activation where required. Depending on the added catalyst deposit and its intended use, the oxide film may be substantially inert or it may have a synergistic effect upon the catalyst material. It should be understood that a suitable promoter or inhibitor may be added to the catalyst material, or incorporated with the reactants undergoing catalytic treatment. For example, a reforming catalyst such as platinum, may be treated with a halide, e.g. HF or BF to improve or promote the catalytic reaction.

It will be observed that the catalyst material, inactivated during processing, may be regenerated in situ. However, when the catalyst is no longer regeneratable and recovery of the catalyst material is desired, the oxide coating with the added catalyst material may be sloughed off from the metal substrate as by electro-chemical means when the substrate is made the cathode in an electrolytic cell. The valuable catalyst material can be recovered by separation from the slough, and the recovered catalyst material may be redeposited on a freshly formed oxide film and used again.

It will be observed that the choice of added catalyst material depends upon the use contemplated. Thus, the catalytic structure of our invention may be advantageously employed in a wide variety of catalytic processes including such typical operations as isomerization, polymerization or alkylation of paraffinic and aromatic hydrocarbons. In addition, the catalytic structure may be useful in the hydration and hydrogenation of olefins, or in the dehydrogenation or oxidation of various organic compounds such as in producing an aldehyde or ketone from the corresponding alcohol, as well as in various cracking reactions and halogenation-dehalogenation processes.

Referring now in greater detail to the catalytic structure of our invention, and the attendant advantages, the extended metal substrate is initially provided with an artifically produced oxide film which is relatively thin as compared to the substrate. The extended metal substrate is not restricted to any particular configuration, and may include metal bars, balls, chain, plates, saddles, sheet, tubes or the like, the members of the substrates not being less than about A; inch in its maximum dimension, and more preferably A inch, and of sufficient thickness on which the oxide film may be adequately produced and still maintain a free metal substrate. Generally an oxide film of about 0.5 to 1 mil is suflicient, but thicker film, or thinner film, may be employed Where desired. The thin oxide film with the added catalyst material defines the depth of the catalyst bed, and therefore limits the extent of diffusion of the reactants through the pores and openings in the bed to this shallow depth. As a consequence, substantially all of the catalyst material is exposed to the reactants, and entrapment of the reactants in the catalyst is minimized or substantially eliminated. In this manner, we readily achieve With less catalyst material a reactive capacity equal to, or greater than, that accomplished by conventional catalysts.

Equally important, the catalytic structure of our invention having a catalyst material deposited thereon functions substantially as an isothermal surface. During a catalytic process, heat transfer in the catalyst bed is readily accomplished by means of the extended metal substrate. Depending on the nature of the reaction, heat may be extracted from, or supplied to, the reactor through the metal substrate thereby providing an adequate means for controlling temperature conditions in the catalyst bed. Thus, in an exothermic process, for example, the metal substrate will conduct the heat to the surroundings of the reactor, and the excess heat extracted therefrom preferably by means of a cooling medium employed in heat exchange relation with the reactor.

In a preferred embodiment of our invention, the catalytic structure is provided in the form of a tube of relatively small inside diameter. The inside diameter of the tube, in general may range from about 0.05 to 0.5 inch, but is dependent upon the type of catalytic reaction, materials undergoing reaction and the capacity of the pumping mechanism to accomplish sufficent turbulence. At least one surface or Wall of the tube, and preferably the interior Wall of the tube, is provided With an oxide film, e.g. an anodically produced oxide film, and the added catalyst material is deposited thereon. The tube through which the reactants pass is preferably of a continuous length sufficient to accomplish the desired catalytic reacspace.

tion in economic yields, but may be coiled to conserve The length of the tube may depend to some extent upon the reaction contemplated, and therefore may be readily determined by one skilled in the art. The wall of the reactor provides adequate support and mechanical strength for the catalyst, and thereby affords a substantially self-sustaining structure. are eliminated as are many of the'structural and supporting features employed in a conventional catalytic reactor.

It will be observed that the metal tube provides an adequate means to control the temperature or heat transfer to or from the catalyst. The metal wall, being a good heat conductor, may be employed as a heat exchanger notwithstanding the relatively thin oxide film. A suitable heat exchange medium may be applied to the exterior wall of the metal tube, for example. During processing, the heat evolved in the catalyst bed is readily conducted by the wall of the tube to the surroundings Where it is absorbed and dissipated by the heat exchange medium. On the other hand, the tubular wall may be employed for supplying heat from a heating medium in the case of an endothermic reaction. It should be understood that in an economic and commercial operation, a number of the catalytic tubes may be housed in parallel in a single unit and arranged in contacting relation with a heat exchange medium.

It is of further significance that in the catalytic tube having a relatively small inside diameter, turbulent flow of the reactants passing through the tube is readily maintained. As a consequence, near maximum reaction rates are achieved. In addition, the catalytic structure of our invention markedly reduces the residence time of the reactants in the reactor, as explained above. Consequently, the reactor may be operated at high temperatures, or optimum temperatures, or, more important, in many cases at higher temperatures and faster reaction rates than those normally encountered in a conventional reactor, without danger of excessive coking or fouling of the catalyst.

The catalytic tube or sheet formed in accordance with the invention is of further advantage in that the reactant gases in certain processes may be caused to pass through the tube or sheet by use of a pervious or permeable tube or sheet, optionally with the application of a pressure differential between the interior and exterior of the tube or opposite sides of the sheet. A porous tube or wall may be formed from powdered metal, preferably sintered, by known procedures in the field of powder metallurgy. Thus, for example, in a hydrogenation process, hydrogen may be diffused through the tube and into immediate contact with the catalyst surface where reaction occurs, thereby more fully utilizing the reactants and increasing the reaction rates.- In other processes, the reactant gases may be caused to pass in or out of the catalyst tube through the permeable wall of the tube.

The following examples will further illustrate our invention.

EXAMPLE 1 Aluminum tubing having a nominal composition of about 2% by weight alloying constituents, the balance being aluminum, was coiled to form two 11 foot sections, each section having an inside diameter of 0.089 inch and a wall thickness of 0.049 inch. The sections of tubing are desirably cleaned on the interior surface by conventional practice as by etching for one minute in a aqueous sodium hydroxide solution at 150 F., rinsing with water, and then immersing in a 35% nitric acid solution for 30 seconds at room temperature and again rinsing with water. The interior wall of the tubing was then anodized in a moving stream of 15% sulfuric acid electrolyte for 60 minutes with a current density of 12 amperes per square foot and at an electrolyte temperature of 6874 F. The interior of the tubing was rinsed with cold water.

The anodic film formed on the interior Wall of the Packed reaction columns tubing sections was impregnated with a cobalt-molyb-' denum-nickel catalyst as follows:

A solution of the catalyst was first prepared by adding to 1500 milliliters of water, 112 grams of nickel sulfate hexahydrate, 73 grams of cobalt sulfate heptahydrate, 89 grams of ammonium molybdate tetrahydrate and grams of ammonium sulfate. The mixture was heated to 180 F., and 500 milliliters of ammonium hydroxide (28.7% by Weight NH OH) was added with stirring to dissolve all the salts.

Both sections of the aluminum tubing were filled with the above solution, each with 12 milliliters, and placed in an autoclave. The ends of the tube remained open. The autoclave was flushed with hydrogen, and then pressurized with hydrogen at 1000 p.s.i.g. at 350 F. and for four hours. Thereafter, the autoclave was depressurized and cooled to room temperature. The tubing sections, upon removal from the autoclave, were dried at F. for two hours under an absolute pressure of 5 p.s.i., and then calcined at 750 F. for two hours in air.

The above procedure was repeated. The net gain in Weight of the tubing was 3.7 grams.

The prepared sections of aluminum tubing were joined to form a 22 foot long tubular reactor. In a hydrogenation treatment, a wax distillate fraction obtained upon distillation of a Mid-Continent paraffinic crude which had been furfural refined to remove a substantial portion of aromatics was employed as the charge stock. The conditions for the reaction are set forth in Table I, below:

Table I Pressure, p.s.i.g 4000 Reactor temperature, F. 625 Liquid space velocity, v./v./hr. 22 Weight space velocity, w./w./hr 111.5 Recycle rate of gas (from high pressure separator) s.c.f./bbl. 12800 From the results, it was found that the color of the charge stock empolyed in the catalytic treatment improved from 20 as measured on a Lovibond colorimeter employing a /2 inch cell to 5 Lovibond 6 inch cell in the product. It will be observed that it was possible to attain an exceptionally high space velocity with a very small amount of active catalyst material under essentially similar conditions as that commonly employed in hydrogenation reactions with conventional catalyst requiring substantially greater quantities of catalyst material.

EXAMPLE 2 Aluminum tubing, in coil form, measuring 10 feet in length, an inside diameter of 0.089 inch, and a wall thickness of 0.049 inch, was anodized on the interior and the anodic film impregnated with a cobalt-molybdenum-nickel catalyst, as in Example 1. The impregnating procedure was performed twice, the tubing showing a net gain in weight of 0.358 grams.

A propylene polymer having a boiling point range of from about 220 F. to 544 F. and an average molecular weight of 224 was hydrogenated by charging the polymer to the tubular reactor under the conditions set forth in Table II, below:

Table 11 Pressure, p.s.i.g 2000 Reactor temperature, F. 650 Contact time, seconds 0.39 Recycle rate of H ft. /bbl. 10000 Double bonds hydrogenated/ second/ square foot reactor surface 1.4 10 Double bonds hydrogenated/second/foot of tube 1.0 10

EXAMPLE 3 An aluminum tube, in coil form, measuring 10 feet in length and having an inside diameter of 0.089 inch and a wall thickness of 0.049 inch was anodized on the interior, as in Example 1. The anodic film was impregnated with a molybdenum oxide film as follows:

A catalyst solution was prepared by adding to 200 milliliters of water, 62 grams of ammonium molybdate tetrahydrate and 33 grams of ammonium sulfate. 30 grams of ammonium hydroxide was added and the solution heated to boiling. The volume of solution was reduced to 250 milliliters by evaporation.

The aluminum tubing was filled with the above solution and placed in an autoclave, the ends of the tube remaining open. The autoclave was flushed with hydrogen, and then pressurized with hydrogen at 3000 p.s.i.g. and at 350 F. for five hours. The autoclave was then depressurized and cooled to room temperature. The aluminum tube was removed from the autoclave, dried at 160 F. for two hours at an absolute pressure of p.s.i., and then calcined at 750 F. for two hours in air. The net gain in weight of the tubing was 1.5 grams.

The treated tubing was employed as a reactor in the oxidation of methanol to formaldehyde. Air, at 74 to 76 F., was used to evaporate the methanol, and the mixture charged to the reactor was preheated to about 710 F. The conditions for the reaction, and the results obtained, are set forth in Table III, below:

Table III Pressure Atmospheric Reactor temperature, F. 710 Contact time, seconds 0.31 Air, ft. /hr. 1.7 Methyl alcohol charged, grams total 20 Formaldehyde recovered, grams total 9.2

Grams formaldehyde/ grams methyl alcohol charged 0.46 Conversion to formaldehyde, wt. percent 48 The formaldehyde was recovered in a water wash tower. Selectivity for the reaction was greater than 90%. The by-products included alcohol, dimethyl ether, acetone and hydrogen.

EXAMPLE 4 Two sections of aluminum tubing, each in coil form, each measuring feet in length and having the same inside diameter and wall thickness of Example 1, were anodized as in Example 1. The sections of tubing were washed with cold water, and then dried at 160 F. The tubes were filled with concentrated phosphoric acid having a concentration of 95% by weight H PO and the excess acid allowed to drain from the tube. The tubular sections were joined to form a foot length reactor, and the tubular reactor was dried in a nitrogen atmosphere at 300 F. for /2 hour. The net gain in weight for the tubes was 2.5 grams.

Isobutylene, technical grade, was polymerized by charging 54 grams of the feed to the tubular reactor under the conditions set forth in Table IV, below:

Table IV Pressure, p.s.i.g 300 Reactor temperature, F. 258290 Liquid space velocity, v./v./ hr 1.4 Liquid product recovered, grams 47 Product distribution (mol percent) Isobutylene 3.3

Dimer 76.7

Trimer 20.0

The products were removed from the reactor as a continuous stream, passed through a water condenser, Dry Ice trap and gas meter, and recovered as liquid. About 7 grams of material was lost in the reaction, the loss occuring during the initial stage of the operation. Product distribution, set forth in the table, shows a conversion of 96.7%.

10 EXAMPLE 5 Six sections of aluminum tubing each measuring 15 feet in length and having an inside diameter of 0.075 inch and a wall thickness of 0.049 inch were anodized as in Example 1. The anodic film of each section was impreg nated with a cobalt-rnolybdenum-nickel catalyst, as in Example 1, and the sections were joined in parallel by an aluminum header means provided with a small U-shaped passage to form a reactor. The reactor was employed in the hydro-cracking of a wax distillate fraction similar to that employed in Example 1, 100% of the distillate fraction having a boiling point above 650 F. The conditions for the hydro-cracking operation are shown in Table V, below:

Table V Pressure, p.s.i.g 1225 Reactor temperature, F 757 Liquid space velocity, v./v./hr 1.7

Recycle rate of gas, s.c.f./bbl 1460 A distillation curve for the product recovery from the hydro-cracking operation showed an initial boiling point of about 212 F. and a boiling point for of the product of about 640 F. This low boiling point range indi cates a high degree of cracking accompanied by hydrogenation.

Aluminum chain of commercial purity, each link of the chain measuring approximately 7 inch, was anodized as in Example 1 and employed as the substrate in Examples 68 below.

EXAMPLE 6 The anodic film on the chain was impregnated with a nickel-tungsten catalyst as follows:

A slurry of tungstic acid was prepared by adding 50 grams of the acid to milliliters of water. milliliters of ammonium hydroxide was added, and the mixture was heated to F. for forty minutes to dissolve the salt. On cooling, a slight precipitate occurred, and therefore an additional 10 milliliters of ammonium hydroxide was added to redissolve any precipitate. A second solution was prepared by dissolving 62 grams of nickel sulfate hexahydrate and 33 grams of ammonium sulfate in 200' milliliters of water. The soluiton was heated to 180 F., and 30 milliliters of ammonium hydroxide was added with stirring. The resulting nickel solution was added to the prepared tungsten solution.

Anodized aluminum chain, weighing 119.7 grams, was placed in a glass tube open at one end and the chain completely submerged with 120 milliliters of the above nickel-tungsten solution. The tube containing the chain and solution was placed in an autoclave, and the anodic film was impregnated with the nickel-tungsten catalyst material by reduction with hydrogen under pressure, as shown in Example 3 and subsequently dried, again as shown in Example 3. The net gain in weight of the chain was 5.7 grams.

The treated chain was employed as the catalyst in the desulfurization-hydrogenation of a vacuum pipe stilled gas oil obtained as part of the overhead from the topping of a California crude and thereby rendered more useful as a cracking stock. The stock had a sulfur content of 1.00% by weight and a carbon residue of 0.41% by weight. Table VI, below, shows the conditions for the reaction.

Table VI Pressure, p.s.i.g 1500 Reactor temperature, F 754 Liquid space velocity, v./v./hr. 0.76

Recycle rate of gas, s.c.f./bbl. 12000 As a result of the reaction, the sulfur content was markedly reduced to 0.39% and the carbon residue reduced to 0.02%. The color was improved from a black for the charge stock to a yellow in the product.

I 1 EXAMPLE 7 Anodized aluminum chain was impregnated with a platinum catalyst as follows:

1.3 grams of chloroplatinic acid hexahydrate was dissolved in 100 milliliters of water and the solution heated at 275 F. for four hours. The pH of the solution was adjusted to 9.2 by the addition of ammonium hydroxide. 120 grams of the aluminum chain were washed twice with 120 milliliters of methyl alcohol, and then dried on a steam plate. The washed and dried chain was placed in a flask, and the flask subjected to vacuum. The prepared ammonium chloroplatinate solution was added to the flask through a separatory funnel and the solution allowed to remain in contact with the chain for one-half hour. The supernatant liquid was evaporated on a steam plate. The chain was then calcined at 910 F. for three hours in air. The chain, impregnated with the platinum material, was immersed in 102 milliliters of an aqueous solution containing 6 grams of hydrogen fluoride dissolved therein, and allowed to stand overnight. The solution was evaporated to dryness on a steam plate, and the chain then calcined at 600 F. for two hours in air. The impregnated catalyst consisted of about 0.22 gram platinum and 0.3 gram fluoride.

The treated chain was used as a catalyst in two separate isomerization runs, the feed stock in each comprising technical grade normal hexane charged to the reactor with 2 cubic feet per hour of hydrogen at a pressure of 500 p.s.i.g. and at a liquid space velocity of 2 v./v./hr. The temperature conditions for each of the two runs, and the products obtained, are set forth in Table VII, below:

EXAMPLE 8 Anodized aluminum chain, weighing 100 grams, was impregnated with a zinc oxide catalyst by pasting from a slurry of the catalyst material as follows:

18.8 grams of zinc oxide and 1.2 grams of sodium carbonate were slurried in 16 milliliters of water, and the anodized chain immersed in the slurry for 15 minutes. The chain was removed from the slurry, and dried for two hours at 350 F. The net gain in weight of the chain was grams. The prepared catalyst was used in the dehydrogenation of isopropanol containing about 99.4% by weight isopropanol, 0.2% acetone and 0.4% water. Table VIII, below, shows the conditions for the reaction, and the products obtained.

T able VIII Pressure Atmospheric Reactor temperature, F: 1 I

Top 667 Middle 775 Bottom 750 Feed, mls. at 83 F. 103 Liquid recovered, mls. at 80 F. 84 Product recovery:

Acetone, percent by weight 70.5 Isopropanol percent by weight 20.6 Water percent by weight 8.9 Ofi gas analysis (after 1 hour):

H 71.2 Acetone 14.6

Propane 12.6 Other hydrocarbons 1.6

12 EXAMPLE 9 Plates or hands of titanium, of commercial purity, measuring 4 inches by /2 by inch, were anodized in a boric acid-ammonia solution having a pH of about 8. Anodization was continued for about 7 minutes at 17 volts with an initial current density of amperes per square foot which leveled oil to 50 to 70 amperes per square foot and at an electrolyte temperature of about 70 to 74 F. The anodized plates were formed into Raehig rings measuring about /2 inch in diameter. In impregnating the anodic film of the rings with a cobalt-molybdenum-nickel catalyst, 44 grams of Raschig rings were placed in an autoclave and covered with 87 milliliters of the catalyst solution prepared in Example 1. The autoclave was flushed with hydrogen, and then pressured with hydrogen at 1000 p.s.i.g, at 350 F. and for five hours. The autoclave was then depressurized and cooled to room temperature. The rings were removed from the autoclave, dried at F. for two hours and then at 750 F. for two hours in air. The net gain in weight of the rings was 9 grams. The impregnated rings were used in a hydrogenation reaction of a wax distillate fraction similar to that employed in Example 1, the conditions for which are set forth in Table IX, below:

Table IX Hours on stream 8 Pressure, p.s.i.g 1125 Reactor temperature, F. 624 Liquid space velocity, v./v./hr. 1.04

Recycle rate of off gas, s.c.f./bbl 5000 The color of the charge stock was improved considerably from 225 as measured in a 6 inch cell on a Lovibond colorimeter to 25 in the final product. Moreover, the sulfur content was reduced from 0.42 percent by weight in the charge stock to 0.10 percent in the product.

EXAMPLE 10 58 grams of fine mesh tantalum wire was anodized under the same conditions as that employed for anodizing the titanium rings of Example 9. The anodized wire was impregnated with a cobalt-molybdenum-nickel catalyst, as shown in Example 9, and the prepared catalyst material was used in the hydrogenation treatment of a wax distillate fraction similar to that employed in Example 1. The conditions for the reaction are shown in Table X, below:

Table X Hours on stream 8 Pressure, p.s.i.g 1133 Reactor temperature, F 624 .Liquid space velocity, v./v./hr. 1.2 Recycle rate of off gas s.c.f./bbl. 5000 The color of the charge stock was improved from 225 Lovibond 6 inch cell to 35 Lovibond 6 inch cell in the product, and the sulfur content reduced from 0.42% by weight to 0.15% in the product.

We claim:

1. A method for preparing a supported catalyst which comprises producing by anodic oxidation an adherent oxide film of at least 0.5 mil thickness integral with the inner wall surface of a metal tubular support as a conduit for reactants undergoing catalysis, forming a solution of a soluble compound of a metal catalyst material, and pressuring said solution with hydrogen at an effective reduction temperature while maintaining said solution in contact with said oxide film thereby depositing said metal catalyst material substantially uniformly on said oxide film on the inner surface of said metal tubular support.

2. A method for preparing a supported catalyst which comprises producing by anodic oxidation an adherent oxide film of at least 0.5 mil thickness integral with the surface of a metal support having an extended surface area and formed from a metal selected from the group consisting of aluminum, titanium, tantalum, zirconium, and hafnium; forming a solution of a soluble compound of a metal catalyst material; and pressuring said solution with hydrogen at an elevated temperature While maintaining said solution in contact with said film thereby depositing said metal catalyst material substantially uniformly on said oxide film.

3. A method for preparing a supported catalyst as defined in claim 2 wherein said solution is an aqueous ammoniacal solution.

References (liter! by the Examiner UNITED STATES PATENTS 7/ 1942 Houghton 252476 X 6/1949 Levine 252-461 X 7/1950 Van der Hoeven 26G667 1/1954 Guyer et al. 252466 1/1957 Bruegger 252-477 8/ 1958 Bente 252-474 FOREIGN PATENTS Great Britain. Great Britain.

OTHER REFERENCES Mellor: Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 16, 1937, Longmans Green & 15 Co., N.Y., page 47.

TOBIAS E. LEVOW, Primary Examiner.

JULIUS GREENWALD, MAURICE BRINDISI,

Examiners. 

1. A METHOD FOR PREPARING A SUPPORTED CATALYST WHICH COMPRISES PRODUCING BY ANODIC OXIDATION AN ADHERENT OXIDE FILM OF AT LEAST 0.5 MIL THICKNESS INTEGRAL WITH THE INNER WALL SURFACE OF A METAL TUBULAR SUPPORT AS A CONDUIT FOR REACTANTS UNDERGOING CATALYSIS, FORMING A SOLUTION OF A SOLUBLE COMPOUND OF A METAL CATALYST MATERIAL, AND PRESSURING SAID SOLUTION WITH HYDROGEN AT AN EFFECTIVE REDUCTION TEMPERATURE WHILE MAINTAINING SAID SOLUTION IN CONTACT WITH SAID OXIDE FILM THEREBY DEPOSITING SAID METAL CATALYST MATERIAL SUBSTANTIALLY UNIFORMLY ON SAID OXIDE FILM ON THE INNER SURFACE OF SAID METAL TUBULAR SUPPORT. 